Three novel anthocyanins, cyanidin 3-O-β-d-glucoside-5-O-(6-O-caffeoyl-β-d-glucoside), cyanidin 3-O-β-d-glucoside-5,3 -bis-O-(6-O-caffeoyl-β-d-glucoside) and cyanidin 3-O-β-d-glucoside-5-O-(6-O-trans-p-coumaroyl-β-d-glucoside), gentiocyanin A, B and C, respectively, were isolated from pink flowers of gentian, along with a known anthocyanin, cyanidin 3-O-β-d-glucoside. The complete structure of each anthocyanin was unambiguously determined by 1D- and 2D-NMR and other spectral methods.